Process for the preparation of sulphones

ABSTRACT

The invention relates to a process for the preparation of compounds of the formula ##STR1## characterized in that the radical X in sulphones of the formula 
     
         X--(CH.sub.2 --CH.sub.2 --O).sub.m --(CH.sub.2).sub.n --SO.sub.2 --CH.sub.2 
    
      --CH 2  OH                                             (2) 
     is replaced by ##STR2## or a compound of the formula ##STR3## is added to the sulphone of the formula 
     
         CH.sub.2 =CH--SO.sub.2 --CH.sub.2 --CH.sub.2 --OH          (3), 
    
     the substituents having the meanings given in the description.

The present invention relates to a process for the preparation ofcompounds of the formula ##STR4## wherein Ar=a phenyl or naphthylradical,

R₁ =H, C₁ -C₄ -alkyl, Cl, Br, C₁ -C₄ -alkoxy or COOH, acylamino, inparticular acetamino or SO₂ -alkylene-OH,

m=0 or 1,

n=2, 3 or 4,

p=0-2,

Z=--CH=CH₂, --CH₂ --CH₂ --OSO₃ H, --CH₂ --CH₂ --S₂ O₃ H, --CH₂ --CH₂--OCOCH₃, CH₂ --CH₂ --OPO₃ H₂ or --CH₂ --CH₂ --OH,

characterised in that the radical X in sulphones of the formula

    X--(CH.sub.2 --CH.sub.2 --O).sub.m --(CH.sub.2).sub.n --SO.sub.2 --CH.sub.2 --CH.sub.2 OH                                             (2)

in which

X=Cl, Br, OCO--(CH₂)₀₋₃ --CH₃ or O--CO--C₆ H₅,

is replaced by ##STR5## or a compound of the formula, in particular ananiline of the formula ##STR6## wherein R₁ and p have the abovementionedmeanings, is added to the sulphone of the formula

    CH.sub.2 =CH--SO.sub.2 --CH.sub.2 --CH.sub.2 --OH          (3).

The resulting compound of the formula ##STR7## in which Z=--C₂ H₄ --OH,

can be converted in the customary manner by functionalisation of the OHgroup into compounds in which Z has one of the other abovementionedmeanings.

In one preferred variant, if p=0, SO₃ H groups are optionallyadditionally introduced into the aromatic radical.

The present invention also relates to sulphones of the formula

    X--(CH.sub.2 --CH.sub.2 --O).sub.q --(CH.sub.2).sub.r --SO.sub.2 --CH.sub.2 --CH.sub.2 OH                                             (6)

wherein

X=Cl, Br, OCO--(CH₂)₀₋₃ --CH₃ or O--CO--C₆ H₅,

q=0 or 1 and

r=2, 3 or 4, if q=1, or

r=3 or 4, if q=0,

and the process for the preparation of sulphones of the formula (6),characterised in that thioethers of the formula

    X--(CH.sub.2 --CH.sub.2 --O).sub.q --(CH.sub.2).sub.r --S--CH.sub.2 --CH.sub.2 --OH                                           (7)

wherein

q and r have the abovementioned meaning,

are oxidised in an aqueous or aqueous-organic solution, preferably withhydrogen peroxide, using tungsten or vanadium compounds as catalysts.

Thioethers of the formula (7) are known and described in severalliterature references:

Tsou et al. Journal of Organic Chemistry 26 (1961) 4987-89,

Su et al. Journal of Organic Chemistry 26 (1961) 4990,

Gilman, Tolman Journal Americ. Soc. 67 (1945) 1848,

D'Agostino, Porter Rapid Commun. Mass. Spectrom. 6 (1992) 717.

They can for example be prepared by one-sided reactions of dihalogenatedcompounds of the formula

    X--(CH.sub.2 --CH.sub.2 --O).sub.m --(CH.sub.2).sub.n --Y  (8)

wherein

X and Y=Cl or Br

and m and n have the abovementioned meanings,

with mercaptoethanol or by the appropriately radical-catalysed addition(see for example Organic Reactions Vol. 13, pages 179 and 189) ofmercaptoethanol to vinyl compounds such as for example vinyl acetate.

The literature also describes the sulphones of the formula (9), U.S.Pat. No. 3,509,218, and of the formula (10), ibidem, and Schoberl,Biedermann, Liebigs Ann. Chemie 716 (1969) 37-46

    Cl--CH.sub.2 --CH.sub.2 --SO.sub.2 --CH.sub.2 --CH.sub.2 OH(9)

    CH.sub.2 =CH--SO.sub.2 --CH.sub.2 --CH.sub.2 OH            (10).

The replacement of the radical X in the sulphones of the formula (2) bya radical, in particular an aniline radical ##STR8## can be carried outin an aqueous, aqueous-organic or purely organic medium, either undercontrolled pH conditions or in the presence of basic media, such as forexample alkali metal carbonate or alkali metal hydrogen carbonate,alkali metal phosphates, alkali metal hydroxide, calcium oxide ormagnesium oxide.

Controlled pH conditions are pH values between 5 and 12. The optimum pHvalue depends on the structure of the sulphone (2).

Solvents which can be used for the substitution reaction are C₁ -C₅-alcohols, acetone, methyl ethyl ketone, N-methylpyrrolidone,dimethylformamide, dimethylsulphoxide or tetramethylenesulphone.

In principle it is possible to carry out the oxidation of the thioetherto form the sulphones (2) and the replacement of the substituent X inthe sulphones to form the compounds of the formula (1) either in anaqueous or an aqueous-organic medium and directly, without anyintermediate isolation of the sulphone (2) being necessary.

The compounds of the formula (1) prepared by the abovementioned processare valuable intermediates for the synthesis of reactive dyestuffs whichare used in particular for dyeing natural and regenerated cellulosefibres.

The compounds of the formula (1) can be used for the synthesis of theabove types of dyestuffs of the formula (4a)

    D--N=N--Ar--NH--(CH.sub.2 --CH.sub.2 --O).sub.m --(CH.sub.2).sub.n --SO.sub.2 --CH.sub.2 --CH.sub.2 --OSO.sub.3 H            (4a)

wherein

D denotes the radical of a diazo component and

m and n have the abovementioned meaning,

using for example diazonium salts as coupling components.

The compounds of the formula (1) are however preferably used for thesynthesis of high fixation bifunctional reactive dyestuffs of theformula ##STR9## wherein Z, R₁, p, m and n have the meaning given undercompound (1) and

X=F, Cl, or Br,

R=H or C₁ -C₄ -alkyl and

Fb=the radical of a dyestuff of the mono- or polyazo, metal complex azo,anthraquinone, phthalocyanine, formazan, azomethine, dioxazine,phenazine, stilbene, triphenylmethane, xanthene, thioxanthone,nitroaryl, naphthoquinone, pyrenequinone or perylene tetracarbimideseries,

by condensation with trihalotriazines and dye bases containing aminogroups.

EXAMPLE 1

A. 129 g of vinyl acetate and 140.4 g of 2-mercaptoethanol are mixedtogether. 1.5 g of azo-bis-(isobutyronitrile) is added with stirring andthe stirring of the mixture is continued, during which the temperatureincreases to 30° C. within about 30 minutes. The mixture is stirredovernight at room temperature and is then heated for 8 hours to 50° C.,until a sample dissolved in DMSO no longer produces the ¹ H-NMR signalsat 7.2 ppm which are characteristic of vinyl acetate (splitting of theindividual CH vinyl proton into a quartet) or those of the CH₂ vinylprotons (each split into doublets) at 4.6 ppm and 4.85 ppm.

A colourless oil is obtained, the main component of which corresponds tothe formula

    CH.sub.3 --CO--O--CH.sub.2 --CH.sub.2 --S--CH.sub.2 --CH.sub.2 --OH

¹ H-NMR in D₆ -DMSO (TMS as the internal standard) ##EQU1##

81.3 g of the thioether of Example 1A in the form of an oil are stirredwith 225 ml of water and 5.25 g of Na acetate; the pH value is adjustedto 5.2 using about 1.5 ml of glacial acetic acid and a catalyst solutionis added which has been obtained from 1.5 g of tungstic acid byneutralising with sodium hydroxide solution in 30 ml of water andadjusting the pH value to 5.2 using 2.4 ml of glacial acetic acid.

90.0 g of 35% hydrogen peroxide are added dropwise at 55° C., the pHvalue being kept at 5.0-5.2 using 2N sodium hydroxide solution.Additional 35% hydrogen peroxide is subsequently added in such an amountthat a slight excess is maintained. A further 20-30 g are usuallyrequired for this purpose. As soon as the total quantity of sulphoxidehas been oxidised to form the sulphone after 4 hours at 55°-60° C., ascan be determined by examining a sample by thin-layer chromatography,the mixture is cooled to 35° C. A colourless solution is obtained.

If the resulting solution is concentrated in vacuo at 35°-40° C., thesubstance

    CH.sub.3 --CO--O--CH.sub.2 --CH.sub.2 --SO.sub.2 --CH.sub.2 --CH.sub.2 --OH

is obtained in the form of a colourless oil which has the followingmasses according to its mass spectrum obtained by chemical ionisation:

M₁ +H⁺ =197

M₂ +H⁺ =155 (cleavage of CH₃ --CO)

M₃ +H⁺ =137 (cleavage of H₂ O)

¹ H-NMR in D₆ -DMSO (TMS as the internal standard) ##EQU2##

C. 84 g of aniline are added to the colourless solution of2-acetoxyethyl-2'-hydroxyethylsulphone (0.45 mol) obtained in Example 1Bat 50° C. The pH value is adjusted to 6.5 with 2N sodium hydroxidesolution and the mixture is stirred for several hours at 55° C. and a pHof 6.5 until the chromatographic examination shows the disappearance ofacetoxysulphone. Excess aniline is then stripped off in vacuo, at50°-60° C., together with the water distilled over, until it disappears,and the product isolated is a brownish oil which gradually solidifies toform a wax-like substance.

Yield: 186 g with a content of 34% (HPLC) of the compound of the formula##STR10##

(Yield of 61% of theory based on the vinyl acetate used in Example 1A).

The isolated and rigorously dried product has the following physicalproperties:

Melting point after rigorous drying: <50C.

Mass spectrum obtained by chemical ionisation: M₁ +H.sup.⊕ =230

¹ H-NMR in D₆ -DMSO (TMS as the internal standard) ##EQU3##

As a secondary component the crude product contains 2-3% ofbis-(2-hydroxyethyl)-sulphone, in addition to 34% of molecular weight229 of the above formula.

EXAMPLE 2

44 g of aniline are added to the colourless solution of2-acetoxyethyl-2'-hydroxyethylsulphone (0.45 mol) obtained in Example1B, the mixture is adjusted to a pH of 7.0 and then stirred for 4 hoursat 50° C. and later at 60° C. until the acetoxysulphone disappears.After concentrating the mixture in vacuo the product described inExample 1C is obtained with a similar content.

EXAMPLE 3

44 g of aniline are added to the colourless solution of2-acetoxyethyl-2'-hydroxyethylsulphone (0.45 mol) obtained in Example 1Band the mixture is maintained at a pH of 6.5 by adding the necessaryquantity of 2N sodium hydroxide solution for 12 hours at 50°-55° C.,until the examination by thin-layer chromatography or HPLC revealsvirtually no remaining content of acetoxysulphone. After concentratingthe mixture in vacuo the N-(2-(2'-hydroxyethylsulphonyl)-ethyl)-anilinedescribed in Example 1C is obtained in a similar form and quality.

EXAMPLE 4

The test of Example 3 is repeated using 66 g of aniline, but otherwiseusing the same procedure and the mixture is worked up by stripping offthe excess aniline, together with water vapour, by vacuum distillation,after which a product corresponding to that of Example 1C is obtained.

EXAMPLE 5

The test of Example 4 is repeated, except that the pH value ismaintained at 5.5 for the purpose of replacing the acetoxy group by theaniline radical.

EXAMPLE 6

The test of Example 4 is repeated, except that the pH value is kept at7.5-8.0 for the purpose of replacing the acetoxy group by the anilineradical.

Additional products of the general formula ##STR11## are obtained whenthe following substituted anilines are used in Examples 2 to 7 insteadof the aniline:

    ______________________________________                                        Example no.   substituted aniline                                             ______________________________________                                        7             o-toluidine                                                     8             p-toluidine                                                     9             m-toluidine                                                     10            p-anisidine                                                     11            m-anisidine                                                     12            o-anisidine                                                     13            p-chloroaniline                                                 14            4-acetaminoaniline                                              15            3-acetaminoaniline                                              16            3-aminobenzenesulphonic acid                                    17            4-aminobenzenesulphonic acid                                    18            2-aminonaphthalene-5-sulphonic                                                acid                                                            19            3-aminophenyl-2'-hydroxyethylsul-                                             phone                                                           20            3-aminobenzoic acid                                             21            4-aminobenzoic acid                                             22            2-aminobenzoic acid                                             ______________________________________                                    

EXAMPLE 23

80.0 g of the sulphone of the formula ##STR12## obtained according toExamples 2-5 are introduced into 40 ml of 96% sulphuric acid at 20°-30°C. and the mixture is stirred for 3 hours. 50 ml of 20% oleum are addeddropwise with cooling at 10°-15° C. and the mixture is stirred for afurther 2-3 hours, until virtually no more starting product can bedetected in the thin-layer chromatogram. The resulting solution ispoured onto 900 g of ice water. 210-220 g of calcium carbonate are thenintroduced into the diluted sulphuric acid suspension until a pH valueof 5.0 is obtained.

After filtering off the calcium sulphate, washing the precipitate andconcentrating the combined filtrates to the required volume, a solutionof the compound ##STR13## is obtained in a yield of 94% (titration withsodium nitrite).

EXAMPLE 24

If the procedure of Example 23 is repeated using identical quantities ofN-(2-(2-hydroxyethylsulphonyl)-ethyl)-aniline, 96% sulphuric acid and20% oleum, and the resulting solution is finally introduced with coolinginto 500 g of ice, and the mixture is subsequently stirred for 1 hour at0°-5° C., a precipitate of the product of the formula ##STR14## isobtained in a yield of 55-65% in the form of a light brown precipitatewhich can be freed from sulphuric acid residues by stirring it intoisopropanol, filtering by suction and washing with isopropanol.

¹ H-NMR in D₆ -DMSO (TMS as the internal standard)

δ=3.43 ppm (2H, t)

δ=3.50 ppm (2H,t)

δ=3.60 ppm (2H,t)

δ=4.11 ppm (2H, t)

δ=7.00 ppm (3H, d, d)

δ=7.30 ppm (2H, t)

δ=8.98 ppm (2H, s)

EXAMPLE 25

A. 81.3 g of 2-acetoxyethyl-2'-hydroxyethyl sulphide from Example 1A aredissolved in 150 ml of N-methyl-2-p-pyrrolidine. A solution of 2.0 g ofsodium tungstate (Na₂ WO₄.2H₂ O) in 10 ml of water, which has beenadjusted to a pH of 5.5 with glacial acetic acid, is added and 90.0 g of35% hydrogen peroxide are introduced at 50° C. with cooling.

The temperature is kept at 50° C. and the pH value is kept at 5.0-5.2with 2N sodium hydroxide solution.

These conditions are maintained and, if necessary, an additionalquantity of hydrogen peroxide required to obtain complete oxidation toform 2-acetyloxyethyl-2'-hydroxyethyl sulphone is added after 2 hours.

B. When the oxidation is complete 44 g of aniline are added. The pHvalue is then maintained at 6.5 and the mixture is stirred for severalhours at 100° C. until the acetoxyethyl compound has disappeared. Asolution of the product of the formula ##STR15## is obtained, The wateris distilled off from the resulting solution in vacuo (1 mm).

C. If 70 g of chlorosulphonic acid are added to the N-methylpyrrolidonesolution of N-(2-(2'-hydroxyethylsulphonyl)-ethyl)-aniline obtainedaccording to Example 25B, the disappearance of the starting product isconfirmed, and the resulting solution is poured onto 300 g of ice withcooling and neutralised with solid lithium carbonate or a 15% sodasolution at 0°-5° C., a solution of the compound ##STR16## is obtainedwhich can be processed further directly.

EXAMPLE 26

45.8 g of N-(2-(2-hydroxyethylsulphonyl)-ethyl)-aniline are introducedat 20°-25° C. into a mixture of 120 ml of 20% and 35 ml of 65% oleum.The solution is heated to 40° C. If the examination of the productreveals no remaining content either of the starting product or of thesulphato compound described in Examples 23, 24 and 25, the reactionsolution is poured onto 900 g of ice and 300 ml of water.

The resulting brown solution is neutralised at 0°-10° C. with about 325g of calcium carbonate until a pH value of 5.5 is obtained. Theprecipitated calcium sulphate is filtered off, washed free of theproduct with water and, after concentration, a brown solution of thecompound of the formula ##STR17## (isomeric sulphonic acids m:p=70:30)is obtained in a yield of 94% (titration with sodium nitrite HCl).

If the solution is evaporated to dryness, a brown, viscous substanceremains which can be converted into a sand-coloured powder bytrituration with isopropanol. The product is dried in an air-circulationcabinet.

¹ H-NMR in D₆ -DMSO (TMS as the internal standard)

    ______________________________________                                                                signal                                                                        integration                                           ______________________________________                                        δ = 3.35 ppm(m, 2H)                                                     δ = 3.42-3.58 ppm(m, 4H)                                                                              8H                                              δ = 4.10-4.16 ppm(m, 2H)                                                δ = 6.58 ppm(d, 2H, p-isomer)                                           δ = 7.40 ppm(d, 2H, p-isomer)                                           δ = 6.63-6.69 ppm(d, d, 1H, m-isomer)                                   δ = 6.90 ppm(s, 1H, m-isomer)                                           δ = 6.95 ppm(d, 1H, m-isomer)                                                                         4H                                              δ = 7.13-7.20 ppm(t, 1H, m-isomer)                                      ______________________________________                                    

EXAMPLE 27

The solution of 2-acetoxyethyl-2'-hydroxyethyl sulphone (0.45 mol)obtained in Example 1B is maintained at a pH of 10 with 2N sodiumhydroxide solution at room temperature for several hours, until theconsumption of sodium hydroxide solution comes to a standstill and theformation of 2-hydroxyethyl-vinyl sulphone is complete. 44 g of anilineare added to the solution, which is heated to 50° C. for 6 hours untilthe addition of aniline is complete. After subsequent concentration invacuo an oil remains, the main component of which consists ofN-(2-(2'-hydroxyethylsulphonyi)-ethyl)-aniline.

EXAMPLE 28

54.4 g of 2-hydroxyethyl-vinylsulphone, produced as described by A.Schoberl and M. Biedermann in Liebigs Ann. Chemie 716, 37-46 (1968) arestirred into 400 ml of water. After adding 45 g of aniline the pH valueis adjusted to 8-9 and the mixture is heated to 50°-55° C. for severalhours until the vinyl compound has be completely converted. Afterremoving the excess aniline with water vapour in vacuo a slowlysolidifying oil of N-(2-(2'-hydroxyethylsulphonyl)-ethylaniline isobtained as a residue with the physical data mentioned in Example 2.

EXAMPLE 29

60.0 g of 3-chloropropyl-2'-hydroxyethyl sulphide, produced by reacting1,3-bromochloropropane with 2-mercaptoethanol (cf. Journal Americ. Soc.67 (1945) 1848) are stirred into 180 ml of water and 4.5 g of sodiumacetate. A solution of 1.2 g of tungstic acid in 30 ml of water and 1.8ml of a 50% sodium hydroxide solution are added and the pH value is thenadjusted to 5.2 with 3.0 ml of glacial acetic acid. 38.7 g of 35%hydrogen peroxide are then added dropwise over a period of 40 minutes at25°-30° C., during which the emulsion initially present is convertedinto a clear solution. An additional 38.7 g of 35% hydrogen peroxide areadded dropwise, during which the temperature is increased to 45°-50° C.and the pH value is kept at 5.2 by adding 6-7 ml of 2N soda solutiondropwise. The mixture is kept at 50° C. for a further 1-11/2 hours ifthe test for H₂ O₂ is positive until no more sulphoxide is detected bychromatographic examination.

The resulting solution can be processed further in its existing form forthe purpose of chlorine substitution. If the isolation of the product isrequired, the reaction solution is evaporated in vacuo in a rotaryevaporator, the residue is taken up in 300 ml of methylene chloride, andthe salts are filtered off by suction, subsequently washed withmethylene chloride and the combined filtrates are evaporated. Thecompound of the formula

    Cl--(CH.sub.2).sub.3 --SO.sub.2 --CH.sub.2 --CH.sub.2 --OH

is obtained in the form of a light yellow oil in a yield of 70.2 g=97%of theory.

¹ H-NMR in D₆ -DMSO (TMS as the internal standard)

δ=2.12-2.24 (m, 2H)

δ=3.23-3.28 (m, 4H)

δ=3.73-3.381 (m, 4H)

δ=about 5.2 (broad, 1H)

EXAMPLE 30

37.9 g of aniline and 34.4 g of sodium hydrogen carbonate are added tothe solution of 70.2 g of 3-chloropropyl-2'-hydroxyethyl sulphoneobtained in Example 29 or a solution of 70.2 g of the isolated sulphonein 280 ml of water. The emulsion is heated to 100° C. for 12 hours,until the chromatographic examination confirms the complete substitutionof the chlorine atom by the aniline radical. Excess aniline is strippedoff by water vapour in vacuo and after sedimentation a brown oil isobtained, which is isolated. After extracting the aqueous phase with 200ml of methylene chloride the isolated oil and the methylene chloridephase are combined, washed with 150 ml of water and dried over sodiumsulphate. After concentrating the methylene chloride solution, finallyin vacuo, 68.0 g=74% of theory of a light brown oil of the formula##STR18## are obtained as the residue: mass spectrum molecular weight M⁺=243

¹ H-NMR in D₆ -DMSO (TMS as the internal standard)

δ=1.92-2.03 (m, 2H)

δ=3.09-3.24 (m, 6H)

δ=3.79-3.85 (m, 2H)

δ=5.08-5.12 (t, 1H)

δ=5.58-5.62 (t, 1H)

δ=6.48-6.58 (m, 3H)

δ=7.04-7.10 (t, 2H)

EXAMPLE 31

64.8 g of N-3-(2-hydroxyethylsulphonyl)-propylaniline from Example 30are added dropwise into a mixture of 54 ml of 96% sulphuric acid and 54ml of 20% oleum over a period of one hour. The temperature of thereaction mixture is maintained at 20°-25° C. by cooling. If, aftersubsequent stirring for 2 to 3 hours, the chromatographic examinationreveals virtually no remaining starting product the mixture is pouredonto 600 g of ice. The solution is neutralised over approximately 11/2hours by adding about 309 g of calcium carbonate until a pH of 5.0 isobtained, the precipitated calcium sulphate is filtered off withsuction, washed with about 2 l of water and the filtrate and washingliquid are concentrated in vacuo at 12-15 mm Hg to a residual volume ofabout 600 ml.

The resulting solution of the compound ##STR19## the content of which isdetermined by titration with a sodium nitrite solution, can be useddirectly for the production of reactive dyestuffs, for example bycondensation with cyanuric fluoride or cyanuric chloride, followed bythe reaction of the condensation product with an amino-group-containingdye base.

If the sulphuric acid half-ester is required to be isolated in the formof a salt, the solution obtained after the precipitation of the calciumsulphate is concentrated after repeated, intermediate filtration, andthe concentrated residue is stirred with isopropanol, filtered off bysuction and dried.

EXAMPLES 32-45

Further products of the general formula ##STR20## are obtained if thefollowing substituted anilines are used in Example 30 instead of theaniline:

    ______________________________________                                        Example no.   substituted aniline                                             ______________________________________                                        32            p-toluidine                                                     33            m-toluidine                                                     34            o-toluidine                                                     35            p-anisidine                                                     36            m-anisidine                                                     37            o-anisidine                                                     38            3-aminobenzenesulphonic acid                                    39            3-aminophenyl-2'-hydroxyethylsul-                                             phone                                                           40            4-aminophenyl-2'-hydroxyethylsul-                                             phone                                                           41            4-acetaminoaniline                                              42            3-acetaminoaniline                                              43            3-aminobenzoic acid                                             44            4-aminobenzoic acid                                             45            3-nitroaniline                                                  ______________________________________                                    

EXAMPLE 46

33.7 g of 4-chloro-1-butyl-2'-hydroxyethyl sulphide, produced byreacting 1,4-dichlorobutane with 2-mercaptoethanol (as described by Tsouet al., J. Org. Chem. 26 (1961), 4989), are stirred into 150 ml of waterand 2.3 g of sodium acetate. After adding 0.6 g of tungstic acid in 15ml of water and 0.9 ml of 50% sodium hydroxide solution, the thioetheris oxidised in the manner described in Example 29 with 41 g of 35%hydrogen peroxide at a final temperature of 45°-50° C. and a solution ofthe sulphone of the formula

    Cl--(CH.sub.2).sub.4 --SO.sub.2 --CH.sub.2 --CH.sub.2 --OH

is obtained, which is reacted, as described in Example 30, after adding20.0 g of aniline and 17 g of sodium hydrogen carbonate at 100° C. toform the compound of the formula ##STR21## which can be isolated in theform of a light brown oil in the manner described in Example 30.

EXAMPLE 47

36.9 g of 2-(2-chloroethoxy)-ethyl-2'-hydroxyethyl sulphide,

¹ H-NMR in D₆ -DMSO (TMS as the internal standard)

δ=2.56-2.62 (t, 2H)

δ=2.68-2.74 (t, 2H)

δ=3.48-3.61 (t, t 4H)

δ=3.66-3.73 (m, 4H)

δ=4.74 (t, 1H),

produced by reacting 2-(bis-chloroethyl) ether with mercaptoethanol, arestirred into 150 ml of water and 2.3 g of sodium acetate and, afteradding a solution of 0.6 g of tungstic acid in 15 ml of water and 0.9 mlof 50% sodium hydroxide solution, the mixture is oxidised with 42 g of35% hydrogen peroxide at temperatures controlled stepwise, initially at30° C. with cooling and in the second stage at 55°-60° C. A solution isobtained from which, after concentration in vacuo, the sulphone of theformula

    Cl--CH.sub.2 --CH.sub.2 --O--CH.sub.2 --CH.sub.2 --SO.sub.2 --CH.sub.2 --CH.sub.2 --OH

is precipitated in the form of a colourless oil: mass spectrum obtainedby chemical ionisation: M+H⁺ =217/219

¹ H-NMR in D₆ -DMSO (TMS as the internal standard)

δ=3.25-3.30 (t, 2H)

δ=3.38-3.43 (t, 2H)

δ=3.69-3.74 (m, 4H)

δ=3.78-3.86 (m, 4H)

δ=4.64 (broad, 1H)

If the aqueous solution of the abovementioned sulphone is notconcentrated and 20.0 g of aniline and 17 g of sodium hydrogen carbonateare added, the mixture is heated to 100° C. and otherwise the sameprocedure is used as described in Example 30, the compound of theformula ##STR22## is obtained, which can be isolated in the form of abrownish oil in the manner described in Example 30: mass spectrumobtained by chemical ionisation: M₁ +H⁺ =274 M₁ +H⁺ --H₂ O=256

EXAMPLE 48

A) 0.15 mol of the compound of the formula ##STR23## are mixed with 100parts of water and 100 parts of ice and the mixture is neutralised withNa₂ CO₃. 0.17 mol of 2,4,6-trifluoro-1,3,5-triazine are added dropwiseto this solution at 0° C. over a period of 10 minutes and the pH ismaintained at 4.5 to 5. 250 parts of a condensation solution of thefollowing compound ##STR24## are obtained.

B) 0.1 mol of the copper complex ofN-(2-carboxy-5-sulphophenyl)-N'-(2'-hydroxy-3'-amino-5'-sulphophenyl)-ms-phenyl-formazan-di-sodiumsalt are dissolved in 600 ml of water. After cooling to 0° to 5° C. thesolution of the component prepared in Example 48A is introduced and thepH value is maintained at 7.0 to 8.0 by adding a soda solution. After 2hours the temperature is allowed to rise gradually to 20° C. and thedyestuff is salted out after the condensation is complete, and theproduct is filtered off and, after buffering at pH 6, dried in vacuo at45° C.

The dyestuff of the formula ##STR25## dyes cotton in a long bath in blueshades with very high fixation yields.

EXAMPLE 49

A) 11.0 g of cyanuric chloride are suspended in 100 ml of ice water. 0.5ml of an emulsifier is added. A solution of 56 mmol of the component ofExample 31 of the formula ##STR26## in 300 ml of water is added dropwiseat 0°-5° C., during which addition the pH value is maintained at 4.2-4.5with 2N soda solution. After removal of small quantities of cyanuricchloride residues the solution of the resulting condensation product isadded to a neutral solution of 0.45 mol of the monoazo compound of theformula ##STR27##

The mixture is maintained at a pH of 6.5 with 2N soda solution. Thetemperature is initially kept at 30° C. for 2 hours, is then raised to40° C. for several hours and finally to 50° C., until the reactionsolution hardly contains any remaining monoazo starting product. Thedyestuff is salted out of the solution using 15% by weight of sodiumchloride, filtered off by suction, washed with a sodium chloridesolution and, after buffering at a pH of 6, dried in vacuo at 45° C. Anorange-coloured powder is obtained.

The dyestuff corresponds to the formula ##STR28## λ_(max) =486 nm inwater.

It dyes cotton in a long bath with a high fixation yield.

We claim:
 1. Process for the preparation of a compound of the formula##STR29## wherein Ar=a phenyl or naphthyl radical,R₁ =H, C₁ -C₄ -alkyl,Cl, Br, C₁ -C₄ -alkoxy or COOH, acylamino, or SO₂ -alkylene-OH, m=0 or1, n=2, 3 or 4, p=0-2, Z=CH₂ CH₂ --OHwherein a sulphone of the formula

    X--(CH.sub.2 --CH.sub.2 --O).sub.m --(CH.sub.2).sub.n --SO.sub.2 --CH.sub.2 --CH.sub.2 OH                                             (2)

wherein X=Cl, Br, OCO--(CH₂)₀₋₃ CH₃ or O--CO--C₆ H₅, is reacted with ananiline of the formula ##STR30## wherein R₁ and p have theabovementioned meanings.
 2. The process according to claim 1, wherein3-chloropropyl-2-hydroxyethyl sulphone is reacted with aniline to give acompound of the formula ##STR31##
 3. Process according to claim 1, inwhich the OH group of a compound of the formula ##STR32## wherein R₁, p,m and n have the meaning given in claim 1, is functionalized formingcompounds in which Z=--CH=CH₂, --CH₂ --CH₂ --OSO₃ H, --CH₂ --CH₂ --S₂ O₃H, --CH₂ --CH₂ --OCOCH₃ or --CH₂ --CH₂.OPO₃ H₂.